CN102280624A - Hydrothermal manufacturing method of manganese-doped zinc oxide composite lithium iron phosphate cathode material - Google Patents
Hydrothermal manufacturing method of manganese-doped zinc oxide composite lithium iron phosphate cathode material Download PDFInfo
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- CN102280624A CN102280624A CN2011101873656A CN201110187365A CN102280624A CN 102280624 A CN102280624 A CN 102280624A CN 2011101873656 A CN2011101873656 A CN 2011101873656A CN 201110187365 A CN201110187365 A CN 201110187365A CN 102280624 A CN102280624 A CN 102280624A
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Abstract
The invention relates to a hydrothermal manufacturing method of a manganese-doped zinc oxide composite lithium iron phosphate cathode material, and the method comprises the following steps: firstly, manufacturing a lithium orthophosphate colloidal solution and a manganese-doped zinc oxide precursor solution respectively; then mixing the lithium orthophosphate colloidal solution with the manganese-doped zinc oxide precursor solution and then stirring sufficiently; and finally adding a ferrous solution to form a lithium iron phosphate precursor solution and placing the lithium iron phosphate precursor solution into an agitated reactor for reaction for 3-30 hours at the temperature of 100-350 DEG C, taking out after samples are cooled naturally, using a great amount of deionized water to wash and drying at the temperature of 80 DEG C to obtain the nano-manganese-doped zinc oxide composite lithium iron phosphate cathode material. In the method, the chemical reactions are carried out in the water solution or steams and other fluids at high temperature and high pressure so as to manufacture the nano-manganese-doped zinc oxide composite lithium iron phosphate cathode material. Compared with a method using a solid state reaction method to generate lithium iron phosphate, the method provided by the invention has the advantages of simplicity in operation, even phase of the product, small grain size of the product and the like.
Description
Technical field
The present invention relates to the new energy materials field, specifically is a kind of hydrothermal preparing process of nano level manganese doping zinc-oxide composite lithium iron phosphate positive electrode.
Background technology
LiFePO4 (LiFePO
4) can be used as anode material for lithium-ion batteries, it is higher that this material has theoretical capacity, and security performance is good, environmental friendliness, and many remarkable advantages such as raw material sources are extensive, and cost of material is low.But this material also exists distinct disadvantage such as electronics and ionic conductance be low, has limited the commercialized development of this material to a certain extent.Theoretical proof, a certain amount of metal cation that mixes in lithium iron phosphate positive material can obviously improve the electronics and the ionic conductance of this material.Mn
2+, Zn
2+With Fe
2+Ionic radius is close, in LiFePO 4 material, add a spot of manganese doping zinc-oxide, not only can in the charge and discharge cycles process, keep the LiFePO4 perfection of lattice, simultaneously, the ZnO dilute magnetic semiconductor material that Mn mixes can significantly improve the electron conductivity of LiFePO4, reduces the decay of lithium iron phosphate positive material in the charge and discharge cycles process.In reaction system, add manganese ion and surfactant, all can reduce the size of LiFePO4 and zincite crystal particle effectively, shorten the evolving path of lithium ion in charge and discharge process.
Hydro thermal method is to carry out chemical reaction by high temperature, high pressure in fluids such as the aqueous solution or steam, a kind of method of preparation powder body material.It can prepare particle diameter is nano level powder body material, compares with solid phase method, has advantages such as simple to operate, that the product thing is even mutually, the product particle diameter is little.
Summary of the invention
The present invention is to provide a kind of hydrothermal preparing process of nano level manganese doping zinc-oxide composite lithium iron phosphate positive electrode.This LiFePO4 is made up of the nanoscale manganese doping zinc-oxide particle that nano level LiFePO4 crystal and LiFePO4 plane of crystal coat.Its concrete implementation step is as follows:
1) preparation lithium phosphate colloid
Phosphorus source, lithium source are mixed, fully stir, form the colloidal solution of lithium phosphate.
2) the presoma LiFePO of preparation manganese doping zinc-oxide
4/ ZnO
1-xMn
x(x ∈ (0,1))
Zinc source, manganese source, surfactant, alkali source are mixed mutually, fully stir in the ice-water bath, form the zinc hydroxide precipitation of mixing manganese.
3) presoma of preparation LiFePO4
With step 2) in precipitation solution slowly drop in the step 1) colloidal solution, fully stir, form solidliquid mixture.To the logical protective gas of mixture system, one side adds source of iron in the solidliquid mixture fast on one side, and vigorous stirring forms cyan solidliquid mixture, feeds protective gas in mixture, moves at last to carry out hydro-thermal reaction in the reactor.
Described phosphorus source is a phosphoric acid, phosphate, as: dibastic sodium phosphate, ammonium dihydrogen phosphate, a kind of in the diammonium hydrogen phosphate, described lithium source is a lithium hydroxide, lithium chloride, lithium acetate, lithium nitrate, a kind of in the lithium sulfate, described source of iron is a ferrous sulfate, frerrous chloride, ferrous nitrate, a kind of in the ferrous oxalate, described zinc source is a zinc acetate, zinc sulfate, a kind of in the zinc chloride, described manganese source is a manganese sulfate, manganese chloride, manganese nitrate, a kind of in the manganese acetate, described surfactant is a polyethylene glycol, a kind of in the polypropylene glycol non-ionic surface active agent, described alkali source is alkali compounds such as alkali and weak acid strong alkali salt, as ammoniacal liquor, lithium hydroxide, NaOH, a kind of in the potassium hydroxide.
In the step 1), in its phosphorus source in phosphate radical and the lithium source mol ratio of lithium be 0.8:1 ~ 1:5.Step 2) in, the addition of mixing manganese zinc oxide is LiFePO
40.5 ~ 10wt%, the addition of surfactant is 0.5 ~ 6 times of molal quantity of zinc in the zinc source, the addition of alkali source is 2 ~ 8 times of zinc molal quantity in the zinc source, the addition in manganese source is 0.001 ~ 0.1 times of molal quantity of zinc in the zinc source.In the step 3), in its source of iron in ferrous iron and the phosphorus source mol ratio of phosphate radical be 0.8:1 ~ 1:1.2.Hydrothermal temperature described in the step 3) is 100 ℃ ~ 350 ℃, and the reaction time is 3 ~ 30 hours.
Description of drawings
Fig. 1: the XRD figure spectrum of nanoscale manganese doping zinc-oxide composite lithium iron phosphate positive electrode of the present invention.
Fig. 2: the SEM figure of nanoscale manganese doping zinc-oxide composite lithium iron phosphate positive electrode of the present invention.
Fig. 3: do not carry out doped iron phosphate crystalline lithium SEM figure.
Embodiment
The present invention is described in detail below by embodiment.
Embodiment 1
[1] gets the LiOH solution 10ml of 1.5mol/L, with the H of 0.5mol/L
3PO
4Solution 10ml splashes in the LiOH solution dropwise, lentamente, fully stirs 1 hour in the ice-water bath, obtains the colloidal solution A of white.
[2] get the Zn (Ac) of 0.5mol/L in addition
2Solution 1ml, the MnCl of 0.01mol/L
2Solution 1ml, the polyglycol solution 0.5ml of 0.5mol/L, the lithium hydroxide solution 1ml of 1.5mol/L mixes the back and continues to stir 2 hours in ice-water bath, obtain the muddy liquid B of white.
[3] under the situation of vigorous stirring, B solution is slowly joined among the A, continue fully to stir 2 hours, form mixed solution C.
[4] get the FeSO of 0.5mol/L
4Solution 10ml adds copperas solution in the mixed solution C fast, stirs 1min, forms cyan mixed solution D.
[5] with behind the mixed solution D feeding nitrogen, move in the reactor, reaction is 16 hours under 180 ℃, with taking a sample, with a large amount of deionized water wash, dries 12 hours down, obtains LiFePO for 80 ℃ behind the natural cooling
4/ ZnO
1-xMn
x(x ∈ (0,1)) powder.
Embodiment 2
Step is identical with step among the embodiment 1, and difference is that the lithium source in [1] is LiCl.
Embodiment 3
Step is identical with step among the embodiment 1, and difference is that the lithium source in [1] is LiCH
3COO.
Embodiment 4
Step is identical with step among the embodiment 1, and difference is that the lithium source in [1] is LiNO
3
Embodiment 5
Step is identical with step among the embodiment 1, and difference is that the phosphorus source in [1] is a dibastic sodium phosphate, and the amount of substance of phosphate radical equals the amount of substance of phosphoric acid among the embodiment 1 in the dibastic sodium phosphate.
Embodiment 6
Step is identical with step among the embodiment 1, and difference is that the phosphorus source in [1] is an ammonium dihydrogen phosphate, and the amount of substance of phosphate radical equals the amount of substance of phosphoric acid among the embodiment 1 in the ammonium dihydrogen phosphate.
Embodiment 7
Step is identical with step among the embodiment 1, and difference is that the phosphorus source in [1] is a diammonium hydrogen phosphate, and the amount of substance of phosphate radical equals the amount of substance of phosphoric acid among the embodiment 1 in the diammonium hydrogen phosphate.
Embodiment 8
Step is identical with step among the embodiment 1, and difference is that the zinc source in [2] is ZnCl
2
Embodiment 9
Step is identical with step among the embodiment 1, and difference is that the zinc source in [2] is ZnSO
4
Step is identical with step among the embodiment 1, and difference is that the zinc source in [2] is Zn (NO
3)
2
Embodiment 11
Step is identical with step among the embodiment 1, and difference is that the manganese source in [2] is MnSO
4
Embodiment 12
Step is identical with step among the embodiment 1, and difference is that the manganese source in [2] is Mn (NO
3)
2
Embodiment 13
Step is identical with step among the embodiment 1, and difference is that the manganese source in [2] is Mn (Ac)
2
Embodiment 14
Step is identical with step among the embodiment 1, and difference is that the surfactant in [2] is a polypropylene glycol.
Embodiment 15
Step is identical with step among the embodiment 1, and difference is that the alkali source described in [2] is an ammoniacal liquor.
Embodiment 16
Step is identical with step among the embodiment 1, and difference is that the alkali source described in [2] is a NaOH.
Embodiment 17
Step is identical with step among the embodiment 1, and difference is that the alkali source described in [2] is a potassium hydroxide.
Embodiment 18
Step is identical with step among the embodiment 1, and difference is that the alkali source described in [2] is a lithium acetate.
Embodiment 19
Step is identical with step among the embodiment 1, and difference is that the divalence source of iron in [4] is a frerrous chloride.
Step is identical with step among the embodiment 1, and difference is that the divalence source of iron in [4] is a ferrous nitrate.
Embodiment 21
Step is identical with step among the embodiment 1, and difference is that the divalence source of iron in [4] is a ferrous oxalate.
Embodiment 22
Step is identical with step among the embodiment 1, and difference is that the protective gas in [5] is an argon gas.
End product XRD diffracting spectrum such as Fig. 1 among the embodiment 1, product is the LiFePO of olivine structural as can be seen
4
End product SEM figure among the embodiment 1 is as Fig. 2, and product is a nano-grade size as can be seen.
Do not carry out doped iron phosphate crystalline lithium SEM figure as Fig. 3, the product particle diameter is bigger as can be seen, is of a size of micron order.
Claims (8)
1. the hydrothermal preparing process of a manganese doping zinc-oxide composite lithium iron phosphate positive electrode is characterized in that the concrete implementation step of this method is as follows:
1) preparation lithium phosphate colloid
Phosphorus source, lithium source are mixed, fully stir, form the colloidal solution of lithium phosphate;
2) presoma of preparation manganese doping zinc-oxide
After zinc source, manganese source, surfactant, alkali source mixing, fully stir in the ice-water bath, form Mn doping zinc-oxide presoma;
3) presoma of preparation manganese doping zinc-oxide
With step 2) in precursor solution slowly drop in the step 1) colloidal solution, fully stir, form solidliquid mixture; Source of iron is added in the solidliquid mixture fast, and vigorous stirring forms cyan solidliquid mixture; in mixture, feed protective gas; move at last and carry out hydro-thermal reaction in the reactor, washing behind the natural cooling, oven dry obtain manganese doping zinc-oxide composite lithium iron phosphate positive electrode.
2. the hydrothermal preparing process of manganese doping zinc-oxide composite lithium iron phosphate positive electrode according to claim 1, it is characterized in that: the phosphorus source described in the step 1) is a kind of in phosphoric acid, dibastic sodium phosphate, ammonium dihydrogen phosphate, the diammonium hydrogen phosphate, and described lithium source is a kind of in lithium hydroxide, lithium chloride, lithium acetate, lithium nitrate, the lithium sulfate.
3. the hydrothermal preparing process of manganese doping zinc-oxide composite lithium iron phosphate positive electrode according to claim 1 is characterized in that: in the step 1), in the phosphorus source in phosphate radical and the lithium source mol ratio of lithium be 0.8:1 ~ 1:5.
4. the hydrothermal preparing process of manganese doping zinc-oxide composite lithium iron phosphate positive electrode according to claim 1, it is characterized in that: step 2) described in the zinc source be soluble zinc salt in the aqueous solution, be a kind of in zinc acetate, zinc sulfate, the zinc chloride, described manganese source is a kind of in manganese sulfate, manganese chloride, manganese nitrate, the manganese acetate, described surfactant is a kind of in polyethylene glycol, the polypropylene glycol, and alkali source is a kind of in ammoniacal liquor, lithium hydroxide, NaOH, potassium hydroxide, the lithium acetate.
5. the hydrothermal preparing process of manganese doping zinc-oxide composite lithium iron phosphate positive electrode according to claim 1 is characterized in that: step 2) in, the addition of zinc oxide is LiFePO
40.5 ~ 10wt%, the addition of surfactant is 0.5 ~ 6 times of zinc molal quantity in the zinc source, the addition of alkali source is 2 ~ 8 times of zinc molal quantity in the zinc source, the addition in manganese source is 0.001 ~ 0.1 times of zinc molal quantity in the zinc source.
6. the hydrothermal preparing process of manganese doping zinc-oxide composite lithium iron phosphate positive electrode according to claim 1; it is characterized in that: in the step 3); source of iron is a kind of in ferrous sulfate, frerrous chloride, ferrous nitrate, the ferrous oxalate, and described protective gas is a kind of in argon gas, the nitrogen.
7. the hydrothermal preparing process of manganese doping zinc-oxide composite lithium iron phosphate positive electrode according to claim 1 is characterized in that: in the step 3), in the source of iron in ferrous iron and the phosphorus source mol ratio of phosphate radical be 0.8:1 ~ 1:1.2.
8. the hydrothermal preparing process of manganese doping zinc-oxide composite lithium iron phosphate positive electrode according to claim 1 is characterized in that: the hydrothermal temperature described in the step 3) is 100 ~ 350 ℃, and the reaction time is 3 ~ 30 hours.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103050695A (en) * | 2012-12-26 | 2013-04-17 | 上海锦众信息科技有限公司 | Preparation method for antimony doped lithium ion battery positive electrode material |
| CN104332603A (en) * | 2014-10-21 | 2015-02-04 | 浙江大学 | Preparation method of lithium manganese phosphate nano sheets and product |
| CN107275638A (en) * | 2017-06-21 | 2017-10-20 | 江苏财经职业技术学院 | Nano-grade lithium iron phosphate composite material and preparation method thereof based on solvent-thermal method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008066019A (en) * | 2006-09-05 | 2008-03-21 | Sumitomo Osaka Cement Co Ltd | Manufacturing method of electrode material, recovery method for lithium, positive electrode material, electrode, and battery |
| CN101244813A (en) * | 2007-02-15 | 2008-08-20 | 比亚迪股份有限公司 | Alkali type iron ammonium phosphate and production method, production method of iron phosphate and production method of ferrous lithium phosphate |
| CN101397131A (en) * | 2008-11-04 | 2009-04-01 | 辽宁石油化工大学 | Method for synthesizing doped type lithium iron phosphate |
-
2011
- 2011-07-06 CN CN2011101873656A patent/CN102280624A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008066019A (en) * | 2006-09-05 | 2008-03-21 | Sumitomo Osaka Cement Co Ltd | Manufacturing method of electrode material, recovery method for lithium, positive electrode material, electrode, and battery |
| CN101244813A (en) * | 2007-02-15 | 2008-08-20 | 比亚迪股份有限公司 | Alkali type iron ammonium phosphate and production method, production method of iron phosphate and production method of ferrous lithium phosphate |
| CN101397131A (en) * | 2008-11-04 | 2009-04-01 | 辽宁石油化工大学 | Method for synthesizing doped type lithium iron phosphate |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103050695A (en) * | 2012-12-26 | 2013-04-17 | 上海锦众信息科技有限公司 | Preparation method for antimony doped lithium ion battery positive electrode material |
| CN104332603A (en) * | 2014-10-21 | 2015-02-04 | 浙江大学 | Preparation method of lithium manganese phosphate nano sheets and product |
| CN107275638A (en) * | 2017-06-21 | 2017-10-20 | 江苏财经职业技术学院 | Nano-grade lithium iron phosphate composite material and preparation method thereof based on solvent-thermal method |
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